In our U.S. Pat. No. 5,073,664 issued Dec. 17, 1991, a process for the coupling of alkanes at low temperature over a regenerable stoichiometric reagent, barium peroxide, is disclosed and claimed. We have now found that by modifying the peroxide by incorporation of transition metal complexes or salts, reactivity is significantly altered even though levels a low as 1% (wt) of a transition metal are added to the peroxide. New reactions have also been discovered depending on the choice of the added metal.